Lubricating oil additive



Patented May 5, 1953 UNITE!) STATES ATENT GFFECE pcsarcs'rrsc OIL. annrrrvs ration of Delaware No. Drawing.

Application December 3%, 1948,

Serial No. 68,377

, l2- Claims.

This invention relates to novel chemical products and to the process for preparing and usin the same. Most particularly it'relates to high molecular weight polymers of diolefinic carboxylic acid esters wherein. the esteriilcation agent is a saturated alcohol. A iurther embodiment ofthe invention is J) so found in copolymers of polymerisaele organic compounds and said diolefinic carbon -ic acid esters. These novel polymers or copolymers are especially useful for improving the pour point and viscosity index other properties of lubricating oils.

One object of the present invention is the production of pour depressants of high potency in a wide variety of lubricating oils. Further objects are the production of additives which are suitable for penetrating oils, extreme pressure lubricants, greases, coating compositions, asphalt wetting agents and the like.

For these products to be active as pour depressants in mineral lubricating oils, it is essential that the polyesters contain long hydrocarbon chains of from 19 to 2 carbon atoms. In the case of simple polymerized esters, the long chain hydrocarbon is generally supplied by a suitable alcohol. Where the product consists of a copolyrner .of a dioleiinic carboxylic acid ester and another polymeric ole compound, it may be supplied by either reactant. In any case, it is necesary that there be present at least one solubilizing hydrocarbon chain longer than Cs, preferably in the C to C29 range. The preferred average chain length of the soluoilising depends somewhat on the lubricating oil with which the prodnot is used. For example, in the case of] light oils of l6! which have been heavily declared to rel sively low pour and cloud; points, relatively rel: "it chain sclub lising groups of Ca and gres. should the Cu. to C14 range, whereas in the case of'more lightly dewaxed product an of $13 to C16 may give optimum po point depression. Solubilizing groups of less t? h Cs have a definite but rela tively smaller ect than the larger groups on the potency of products as pour depressants. It has also been found that different size groups are required if the groups are highly branched such as those derived from alcohols prepared by the Oxo reaction of polypropylene with carbon monoxide and hydrogen.

Among the esters which may be employed are those of sorbic acid,

CH3--CH CH--CH::CH-COOH beta vinyl acrylic acid,

(re ortage-escapees and other alpha beta unsaturated diolefiuic acids. It is preferred to employ acids in which the number of carbon atoms is between 5 and about 19, the upper limit being by the ease, of polymerization or copolymerizatcn. lChe straight chain acids are preferred, although slightly branched acids are also suitable, particularly if branching occurs on the alpha carbon atom to the carhoxyl group. The unsaturated acids that have two olcfinic groups in a conjugated system are particularly useful.

Particularly suitable as an esterification agent is a commercially available mixed alcohol obtaincd by hydrogenation of coconut oil. This product is. sold under the trade name Lorol and is a mixture of saturated straig chain alcohols ranging from 10 to 18 carbon atoms but having a major proportion of lauryl alcohol which has 12 carbon atoms. Other related products are by separating this material, which may considered as a crude mixture, into several different fractions having a relatively higher proportion of the higher, lower, or medium constituent thereof. The composition of Lorol per se and related products, Lorol B and Lorol R, is approximately as follows:

Composition of mixtures of commercial alcohols Copolymcrs of the. above esters are obtained by reaction with va'ious; types of unsaturated materials among which are vinyl esters, vinyl halides, vinyl ethers, vinyl lretones, 'iuinarates, maleates, itaconates, acrylates, methacrylates, styrene and the like. It long straight chains are provided in the co-monomers, greater freedom may be exercised in using short chain esters of the cliolefinic acid.

It is further within the comprehension of this invention to react the poly Hers or copolymers with various reagents which will combine with either part or all of the remaining olefinic groups. Among these reagents are sulfuric acid and fuming sulfuric acid which yield sulfates or sulfonates, thus providing a possibility of producing metal salts, for example, those of Ba, Ca, or, Mg, Al, etc., which are useful as lubricating oil additives. Sulfur halides or phosphorus sulfides may also be combined with the olefinic groups.

3 In the case of the products from the phosphorus s fides, metal salts may be prepared which are valuable as lubricating oil additives.

Various methods of polymerization and copclymerization may be used, involving either mass or emulsion technique. Heat and pressure may be used with or without the presence of a catalyst. In the mass polymerization or copolymerizations such catalysts as peroxides, light, oxygen, ozone, clay, boron fluoride, aluminum chloride, sodium and the like may be used. Benzoyl peroxide is generally preferred for this reaction.

The reaction is generally accomplished in a period ranging from 2 to 100 hours, depending on catalyst and temperature conditions which may range from 50 to 150 C. Inert solvents such as naphtha, light lubricating oil, chloroform, and the like may be used in order to control re" action rate or product molecular weight, but are not generally required.

The invention will better be understood from a consideration of the following examples:

Example I A 3 liter three-necked flask equipped with a water trap and a reflux condenser was charged with 353 g. sorbic acid (3.15 mols), 625 g. Lorol B alcohol (3.0 mols), 3 g. of sulfosalicylic acid and 500 c. of naphtha. The above mixture was refluxed for 21 hours during which 52.5 cc. of water was collected. The reaction product was diluted with 500 cc. of benzol and was given three washes with a 5% solution of sodium carbonate in water. The solvents were substantially removed by first heating on a steam bath followed by the use of nitrogen and a vacuum at 100 C. The resulting ester had a saponification value of 186 and a neutralization number of 1.66 and a viscosity of 46.5 SUS at 210 F.

Three samples of the above ester were charged in a x 200 mm. test tube from which air was displaced by means of nitrogen. Catalyst was added to each and the resulting mixtures blown again with nitrogen until the catalyst was dissolved. The test tubes were stoppered and placed in an oven for polymerization. The temperature and catalyst specifications for polymerizing the above samples are as follows:

n. Polymer 2 8 2 Weight Percent Catalyst SUS Sample A 60 66 5.0 benzoyl peroxide". 339 Sample B 115 10 0.0 240 Sample 0.-.. 125 16 4.0 curncne hydro- 439 peroxide.

Example II Example III Cetyl ester of sorbic acid was prepared in accordance with procedure of Example I. A sam- At the end of the time, the resulting ple of cetyl sorb-ate was charged in a test tube, the tube was then stoppered and placed in an oven at 100 C. for 66 hours. At the end of this time the resulting polymers had a viscosity of 390 SUS at 210 F.

Example IV n-Tetradecyl ester of sorbic acid was prepared in accordanc with the procedure of Example I. A test tube was charged with n-tetradecyl sorbate and the air displaced with nitrogen by blowing, after which 5.0 weight per cent of powdered benzoyl peroxide was added. The resultant mixture was again blown with nitrogen until the peroxide was dissolved. The test tube was then stoppered and placed in an oven at 80 C. for 16 hours. At the end of this time, the resulting polymer had a viscosity of 305 SUS at 210 F.

Example V Samples of n-octyl sol-bate and stenol sorbate were prepared in accordance with the procedure of Example I. A mixture containing 48 weight per cent n-octyl sorbate and 52 weight per cent stenol sorbate was charged in a test tube and polymerized in accordance with the procedure of Example I, using 5.0 weight per cent benzoyl peroxide as a catalyst and heating to 80 C. for a period of 16 hours.

Example VI Samples oi n-decyl sorbate and n-tetradecyl sorbate, prepared in accordance with Examples and IV, were mixed together to obtain a solu tion containing weight per cent n-decyl sorhate and 55 weight per cent of n-tetradecyl sorbate and polymerized in accordance with procedure of Example I, using 5.0 weight per cent benzoyl peroxide as a catalyst and heatin to a temperature of 80 C. for a period of 16 hours.

Example VII A mixture of 80 weight per cent Lorol B sorbate, obtained in accordance with the procedure of Example I, and 20 weight per cent of vinyl acetate were charged in a test tube and copolymerized in accordance with the procedure described in Example I, using 5.0 weight per cent benzoyl peroxide as a catalyst and heating to a temperature of 80 C. for a period of 42 hours.

Example VIII A copolymerized product of 80 weight per cent Lorol B sorbate and 20 weight per cent styrene was obtained following the procedure of Example VII, heating to a temperature of 80 C. for a period of 18 hours. The resulting product had a viscosity of 560 SUS at 210 F.

Example IX Example VIII was repeated, using weight per cent Lorol B sorbate and 30 weight per cent styrene. The resulting copolymer had a viscosity of 1440 SUS at 210 F.

Example X Example IX was repeated, using a mixture of Weight per cent Lorol B sorbate and 20 weight per cent methyl acrylate. The reaction time was 42 hours and the resulting copolymer had a viscosity of 471 SUS at 210 F.

Example XI Example X was repeated, using a mixture of 80 weight per cent Lorol B sorbate and 20 weight per cent butyl itaconate. The resulting copolymer had a viscosity of 182 SUS at 210 F.

The polymeric materials obtained by the procedures of Example I to XI were evaluated by blending in test oils and. the pour points of the 5 blends obtained by standard AS-TM methods. The test oils used. had the following characteristics: Oil A was a Pennsylvania 180 neutral; oil B was an extracted Mid-Continent neutral plus bright stock having a viscosity index of 103 and a viscosity of 46.1 SUS at 210 F.; oil C was a Mid-Continent neutral plus 3.5% Pennsylvania bright stock; Oil D was an extracted Mid-Continent neutral plus bright stock and having a viscosity index of 114 and viscosity of 46 S138 at 210 F. The blends were evaluated with the following results:

Polymer ASTM Pour Point, F. Composition zf Percent 2 8 9;

Neutral Test Oil +10 +20 +30 +5 Lorol B sorbate, Sample A..." 0.2 20 +30 20 Lorol B sorbate, Sample 13..-. 0.5 Lorol B sorbate, Sample 0 1 0.1 n-D ecyl sorbate 0. 5 Getyl Sorbate. 0.5 n-Tetradecyl sorbate 1 0. 5 0.1 n-Octyl sorbate, 48% 0 5 Stenol sorbate, 52% 3O n-Decyl sorbate, 45%. 0.5 1O 20 +30 ii-Teiirgdecytrl serial; 55% 1 0. 1 +10 oro sat a e, g ,56 0. 2 -15 -20 +30 oro sor ate i i lg 0. 2 -5 -5 +30 oro sor a e, 70 a i g t f o 2 -5 +10 +30 etc sor a e, gethlyfiacqgag 0.2 15 20 +30 oro sor a e, Butyl itaconate, 20 2 0 +10 +30 1 Unreacted monomer extracted.

What is claimed is:

1. A polymeric material consisting of the polymerization product of an ester of a C5 to C10 alpha beta unsaturated diolefinic carboxylic acid wherein the alcohol radical of the ester group contains from 8 to 18 saturated carbon atoms and a polymerizable compound selected from the class consisting of said ester and vinyl esters and vinyl ethers.

2. A product consisting of a copolymer of a polymerizable organic compound containing a vinyl group selected from the class consisting of vinyl esters and vinyl ethers and an ester of a C5 to C10 alpha beta unsaturated diolefinio carboxylic acid having from 5 to 10 carbon atoms wherein the alcohol radical of the ester group contains from 8 to 18 saturated carbon atoms.

3. A product consisting of a copolymer of vinyl acetate and an ester of a C5 to C10 alpha beta unsaturated diolefinic carboxylic acid wherein the alcohol radical of the ester group contains from 12 to 16 carbon atoms.

4. A product consisting of a copolymer of a vinyl acetate and a hydrogenated coconut oil alcohol ester of sorbic acid.

5. A composition consisting essentially of a mineral lubricating oil having combined therein from 0.05 to 10% of a polymerized ester of a C5 to C10 alpha beta unsaturated diolefinic carboxylic acid, the alcohol radical of said ester group containing from 8 to 18 carbon atoms.

6. A composition consisting essentially of a mineral lubricating oil and from 0.05 to 10% by weight based on the oil of a copolymer of a polymerizable organic compound containing a vinyl group selected from the class consisting of vinyl esters and vinyl ethers and an ester of a Cs to C10 alpha beta unsaturated diolefinic carboxylic acid, the alcohol radical of said ester group containing from 8 to 18 carbon atoms.

7. A composition consisting essentially of a mineral lubricating oil having combined therein from 0.05 to 10% by Weight based on the lubrieating oil of a polymerized ester of sorbic acid wherein the alcohol radical of the ester group consists of 8 to 18 saturated carbon atoms.

8. A composition as in claim 7 wherein the alcohol radical of the ester group consists of 12 to 16 saturated carbon atoms.

9. A composition consisting essentially of a mineral lubricating oil and 0.05 to 10% by weight based on the oil of a hydrogenated coconut oil alcohol ester of sorbic acid.

10. A composition consisting essentially of a mineral lubricating oil having combined therein from 0.05 to 10% by Weight based on the lubricating oil of a copolymer of vinyl acetate and an ester of sorbic acid wherein the alcohol radical of the ester group contains from 8 to 18 linear saturated carbon atoms.

11. A composition as in claim 10 wherein the alcohol radical of the ester group contains from 12 to 16 carbon atoms.

12. A mineral lubricating oil containing a minor amount of a polymerized ester of sorbic acid corresponding to the formula CH3CH=CH-CH=CH+COOR where R is an alkyl group of from 10 to 18 carbon atoms.

13. As a new composition of matter a polymerized ester of sorbic acid corresponding to the formula where R is an alkyl group having from 10 to 18 carbon atoms.

JEFFREY H. BARTLETT.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,149,857 Mikeska Mar. 7, 1939 2,327,705 Frolich Aug. 24, 1943 2,342,113 Blair Feb. 22, 1944 2,363,792 Jahn Nov. 28, 1944 2,375,516 Blair May 8, 1945 FOREIGN PATENTS Number Country Date 387,381 Great Britain Feb. 6, 1933 739,082 Germany Aug. 5, 1943 OTHER REFERENCES Hautz et al.: Jour. Am. Chem. Soc.. 1614 (1933), 55. 

12. A MINERAL LUBRICATING OIL CONTAINING A MINOR AMOUNT OF A POLYMERIZED ESTER OF SORBIC ACID CORRESPONDING TO THE FORMULA 